JP5264768B2 - Method for coating a metal strip - Google Patents
Method for coating a metal strip Download PDFInfo
- Publication number
- JP5264768B2 JP5264768B2 JP2009543402A JP2009543402A JP5264768B2 JP 5264768 B2 JP5264768 B2 JP 5264768B2 JP 2009543402 A JP2009543402 A JP 2009543402A JP 2009543402 A JP2009543402 A JP 2009543402A JP 5264768 B2 JP5264768 B2 JP 5264768B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- mol
- coating
- use according
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000576 coating method Methods 0.000 title claims description 43
- 239000011248 coating agent Substances 0.000 title claims description 38
- 229910052751 metal Inorganic materials 0.000 title claims description 38
- 239000002184 metal Substances 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 16
- 229920000728 polyester Polymers 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 24
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- -1 aliphatic dicarboxylic acids Chemical class 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 13
- 239000001361 adipic acid Substances 0.000 claims description 12
- 235000011037 adipic acid Nutrition 0.000 claims description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 6
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 claims description 3
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 3
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004640 Melamine resin Substances 0.000 claims description 3
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000002216 antistatic agent Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 239000006082 mold release agent Substances 0.000 claims description 3
- 239000003504 photosensitizing agent Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 239000003380 propellant Substances 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 239000013008 thixotropic agent Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 2
- BUYHVRZQBLVJOO-UHFFFAOYSA-N 2-ethyl-2,4-dimethylhexane-1,3-diol Chemical compound CCC(C)C(O)C(C)(CC)CO BUYHVRZQBLVJOO-UHFFFAOYSA-N 0.000 claims description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 2
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- 229940100573 methylpropanediol Drugs 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 81
- 235000011118 potassium hydroxide Nutrition 0.000 description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 239000003973 paint Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 208000028626 extracranial carotid artery aneurysm Diseases 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000000825 ultraviolet detection Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- 235000009161 Espostoa lanata Nutrition 0.000 description 1
- 240000001624 Espostoa lanata Species 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004018 waxing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2252/00—Sheets
- B05D2252/02—Sheets of indefinite length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、金属帯材を被覆するための、ポリエステルベースの分枝鎖非晶質マクロポリオールの使用、金属帯材を被覆するための方法並びにそれにより得られた被覆された金属帯材に関する。 The present invention relates to the use of polyester-based branched amorphous macropolyols for coating metal strips, to a method for coating metal strips and to the coated metal strips obtained thereby.
背景技術
金属帯材の被覆系は、例えばアルミニウム又は鋼からなる巻き取られた金属薄板に、極めて短時間に、即ち経済的に、高価値の被覆を設けるために使用される。他の被覆法、例えば噴霧と比較して、前記方法は顕著な利点を示す。例えば、ここでは品質的に高価値の均一の被覆が高収率でかつわずかな排出物で達成される。
Background of the Invention Metal strip coating systems are used to provide high-value coatings on wound metal sheets, for example made of aluminum or steel, in a very short time, ie economically. Compared to other coating methods, such as spraying, the method shows significant advantages. For example, here a uniform coating of high quality is achieved in high yield and with little emissions.
金属帯材の被覆は、連続法である。金属帯材の端部で被覆プロセスの更なる進行を保証するためにいわゆる蓄電池が使用され、それによって、次の金属帯材を投入する時点で、帯材を限定された期間内に更に送ることができる。金属帯材は一般に予め清浄化され、前処理され、かつ両面にプライマーが施与される。金属帯材を被覆するためには、例えば、有機溶剤中の、ヒドロキシル基含有バインダー、例えばポリエステル及びブロックトポリイソシアネート及び/又はメラミン樹脂及びその誘導体の溶液からなる、液体の熱硬化性被覆剤が使用される。他の成分として、顔料及び他の添加剤が挙げられる。 The coating of the metal strip is a continuous process. So-called accumulators are used to guarantee further progress of the coating process at the end of the metal strip, so that the strip is fed further within a limited period of time when the next metal strip is introduced. Can do. Metal strips are generally pre-cleaned, pretreated and primed on both sides. In order to coat the metal strip, for example, a liquid thermosetting coating comprising a solution of a hydroxyl group-containing binder, for example polyester and blocked polyisocyanate and / or melamine resin and derivatives thereof in an organic solvent. used. Other components include pigments and other additives.
金属帯材の被覆系に関する重要な特性は、例えば耐候性、耐加水分解性、耐化学薬品性及び耐引掻性、高い光沢、硬度及び可撓性である。支持体が、塗布プロセス後に、1以上の成形工程、例えば多くの部材のために必要であるような深絞り加工に供される場合、可撓性は、被覆の付着特性に強度に影響を及ぼす。 Important properties regarding the coating system of the metal strip are, for example, weather resistance, hydrolysis resistance, chemical resistance and scratch resistance, high gloss, hardness and flexibility. When the support is subjected to one or more molding steps after the application process, such as deep drawing as is necessary for many components, flexibility affects the adhesion properties of the coating. .
耐候性は特に、表面が直接太陽光及びその他の気候の影響に曝される部材(これにはとりわけ交通標識、ファサード部材、ガレージ扉、雨受け及び車両部材等が含まれる)にとって重要である。 Weather resistance is particularly important for components whose surfaces are directly exposed to sunlight and other climatic effects, including, among others, traffic signs, facade members, garage doors, rain pans and vehicle components.
原則的に、支持体付着は、比較的軟質の、及び比較的可撓性の高いバインダーの場合により良好であり、別の面では、耐候性及び耐久性は比較的硬質のバインダーの場合により良好である。 In principle, substrate adhesion is better with relatively soft and relatively flexible binders, and in other respects weatherability and durability are better with relatively hard binders. It is.
前記の全ての特性の他に、金属帯材の被覆の際に、経済性というファクターは極めて重要である。単位時間当たりに可能な限り長い金属帯材の区間を被覆することを目指すべきである。この場合、制限されるパラメータは、炉内での金属帯材の滞留時間ないし必要な炉温度であり、それによって塗料の完全な架橋が達成される。このように被覆された薄板の炉内滞留時間が短縮されること、即ち、使用されるポリマーの分子量が小さいほど、即ち、架橋性基、例えばヒドロキシル基の密度が高い程、使用されるバインダーの架橋反応性が向上することは一般的な知識水準である。しかしながら、特にメラミン化合物を架橋剤として使用する場合には、分子量のアトランダムな低下及びこれに伴う高い架橋密度と、金属帯材の被覆にとって認容不可能な完成塗料の脆化とが相対している。 In addition to all the above properties, the factor of economy is very important when coating metal strips. It should aim to cover as long a section of metal strip as possible per unit time. In this case, the limiting parameter is the residence time of the metal strip in the furnace or the required furnace temperature, whereby a complete crosslinking of the paint is achieved. The residence time in the furnace of the coated thin plate is shortened, that is, the lower the molecular weight of the polymer used, that is, the higher the density of crosslinkable groups such as hydroxyl groups, the higher the binder used. It is a general knowledge level that cross-linking reactivity is improved. However, especially when melamine compounds are used as crosslinkers, the relative decrease in molecular weight and the resulting high crosslink density, and the embrittlement of the finished paint, which is unacceptable for coating metal strips, are relative. Yes.
比較的短い焼付時間を、同様に高められた炉温度により達成することができる。これに伴う望ましくないより高いエネルギーコストに加えて、任意の高い温度は、多くの支持体では実現不可能である。いわゆるBH鋼("bake hardening":焼付硬化)は、例えばより高い温度で硬化するため、この理由から更に成形工程に供することができない。 A relatively short baking time can be achieved with a similarly increased furnace temperature. In addition to the undesirably higher energy costs associated with this, arbitrarily high temperatures are not feasible with many supports. So-called BH steel ("bake hardening") is hardened at higher temperatures, for example, and cannot be subjected to further forming processes for this reason.
経済性及び塗料品質に関する特性要求を保証するために、従来技術(WO 2004/039902)では、分枝鎖の比較的低分子のバインダーと高分子の主に直鎖のバインダーとの混合物が、可撓性付与のために、架橋剤と共に金属帯材の被覆において使用されている。この種の配合物を用いて、塗料が炉内で十分に高い架橋反応性を有することを保証することができる。 In order to guarantee the economic and paint quality characteristic requirements, the prior art (WO 2004/039902) allows a mixture of branched relatively low molecular weight binders and high molecular weight mainly linear binders. It is used in coating metal strips with a cross-linking agent to provide flexibility. This type of formulation can be used to ensure that the paint has a sufficiently high cross-linking reactivity in the furnace.
2種の異なるバインダーを製造しなければならず、かつ最終的に、好適な比で塗料の配合物に混合しなければならないことは、単一のバインダーをベースとする塗料配合物に対して著しい経済的な欠点と同じ意味をもつ。この理由から、本発明の課題は、上記の塗料特性をもたらし、それと同時に高い架橋反応性をももたらし、その結果、中程度の架橋剤量で可能な限り低い炉内滞留時間を可能にする金属帯材を被覆するための方法を開発することであった。OH末端ポリエステルの架橋反応性がOH価の増加に伴って向上することは一般に公知である。しかしながら、高いOH価、即ち低い分子量を有するポリエステルは、可撓性の不足に基づき金属帯材の被覆に使用不可能な脆い塗料を招く。 The fact that two different binders must be manufactured and ultimately mixed into the paint formulation in a suitable ratio is significant for single binder-based paint formulations It has the same meaning as an economic disadvantage. For this reason, the object of the present invention is to provide the above-mentioned paint properties and at the same time also a high cross-linking reactivity, so that a metal with a moderate cross-linker amount and the lowest possible residence time in the furnace. It was to develop a method for coating the strip. It is generally known that the crosslinking reactivity of OH-terminated polyesters increases with increasing OH number. However, polyesters with high OH numbers, ie low molecular weights, lead to brittle paints that cannot be used for coating metal strips due to lack of flexibility.
意想外にも、アルコール成分に対して10〜25モル%の三官能性分枝化剤含分を有し、かつ分子量が2500〜4500g/モルである分枝鎖ポリエステルが、金属薄板の被覆に十分な、高い架橋反応性と可撓性との均衡を示すことが判明した。この種の分枝鎖ポリエステルはEP 1479709に記載されている。 Surprisingly, a branched polyester having a trifunctional branching agent content of 10 to 25 mol% with respect to the alcohol component and having a molecular weight of 2500 to 4500 g / mol is suitable for coating a thin metal sheet. It has been found that a sufficient balance of high cross-linking reactivity and flexibility is exhibited. This type of branched polyester is described in EP 1479709.
これに応じて、本発明の対象は、金属帯材を被覆するための、カルボン酸成分、及び、アルコール成分に対して少なくとも三官能性のアルコール10〜25モル%と少なくとも1の他のアルコール75〜90モル%とからの少なくとも1のアルコール成分を、架橋試薬の存在下に反応させることにより得られたポリエステルベースの分枝鎖非晶質マクロポリオールの使用であって、その際、ポリエステルは、以下
・2500〜4500g/モルのMn
・0〜200mgKOH/gのOH価、及び
・0〜10mgKOH/gの酸価
を有するものとする、使用である。
Accordingly, the subject of the present invention is a carboxylic acid component and at least a trifunctional alcohol 10-25 mol% and at least one other alcohol 75 for coating the metal strip with respect to the alcohol component. Use of a polyester-based branched amorphous macropolyol obtained by reacting at least one alcohol component from ˜90 mol% in the presence of a crosslinking reagent, wherein the polyester is the following · 2500~4500g / mol of M n
• Use with an OH number of 0-200 mg KOH / g and an acid number of 0-10 mg KOH / g.
本発明により使用されるポリエステルベースの分枝鎖非晶質マクロポリオールは、出発酸成分として、少なくとも1の芳香族及び/又は脂肪族ジカルボン酸及び/又はポリカルボン酸、例えばフタル酸、イソフタル酸、テレフタル酸、脂環式1,2−ジカルボン酸、例えば1,2−シクロヘキサンジカルボン酸及び/又はメチルテトラヒドロフタル酸、テトラヒドロフタル酸及び/又はメチルヘキサヒドロフタル酸、コハク酸、セバシン酸、ウンデカン二酸、ドデカン二酸、アジピン酸、アゼライン酸、ピロメリット酸、トリメリット酸、イソノナン酸及び/又は二量体脂肪酸を含有する。イソフタル酸、1,2−シクロヘキサンジカルボン酸、フタル酸及びアジピン酸が有利である。 The polyester-based branched amorphous macropolyol used according to the invention has at least one aromatic and / or aliphatic dicarboxylic acid and / or polycarboxylic acid as starting acid component, for example phthalic acid, isophthalic acid, Terephthalic acid, cycloaliphatic 1,2-dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid and / or methyltetrahydrophthalic acid, tetrahydrophthalic acid and / or methylhexahydrophthalic acid, succinic acid, sebacic acid, undecanedioic acid , Dodecanedioic acid, adipic acid, azelaic acid, pyromellitic acid, trimellitic acid, isononanoic acid and / or dimer fatty acids. Preference is given to isophthalic acid, 1,2-cyclohexanedicarboxylic acid, phthalic acid and adipic acid.
各酸成分は、部分的にか又は完全に、無水物及び/又は低分子アルキルエステル、有利にメチルエステル及び/又はエチルエステルからなることができる。 Each acid component can consist partly or completely of anhydrides and / or low molecular alkyl esters, preferably methyl esters and / or ethyl esters.
少なくとも三官能性のアルコール成分として、例えばトリメチロールプロパン、トリメチロールエタン、1,2,6−トリヒドロキシヘキサエリトリット、グリセリン、トリスヒドロキシエチルイソシアヌレート、ペンタエリトリット、ソルビット、キシリット及び/又はマンニットを、アルコール成分に対して10〜25モル%の量で使用することができる。 As at least trifunctional alcohol components, for example, trimethylolpropane, trimethylolethane, 1,2,6-trihydroxyhexaerythritol, glycerin, trishydroxyethylisocyanurate, pentaerythritol, sorbit, xylit and / or mannitol Can be used in an amount of 10 to 25 mol% with respect to the alcohol component.
それに加えて、アルコール成分は、他の直鎖及び/又は分枝鎖、脂肪族及び/又は脂環式及び/又は芳香族ジオール及び/又はポリオールを含有することができる。有利に、付加的なアルコールとして、エチレングリコール、1,2−プロパンジオール及び/又は1,3−プロパンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、テトラエチレングリコール、1,2−ブタンジオール及び/又は1,4−ブタンジオール、1,3−ブチルエチルプロパンジオール、1,3−メチルプロパンジオール、1,5−ペンタンジオール、ビスフェノールA、ビスフェノールB、ビスフェノールC、ビスフェノールF、ノルボルニレングリコール、1,4−ベンジルジメタノール及び1,4−ベンジルジエタノール、2,4−ジメチル−2−エチルヘキサン−1,3−ジオール、シクロヘキサンジメタノール、ジシドール、ヘキサンジオール、ネオペンチルグリコールが、アルコール成分に対して75〜90モル%の量で使用される。 In addition, the alcohol component can contain other linear and / or branched, aliphatic and / or alicyclic and / or aromatic diols and / or polyols. Preferably, as additional alcohols, ethylene glycol, 1,2-propanediol and / or 1,3-propanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,2-butanediol and / or Or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, norbornylene glycol, 1 1,4-benzyldimethanol and 1,4-benzyldiethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol, cyclohexanedimethanol, dicidol, hexanediol, neopentyl glycol It is used in an amount of 75 to 90 mol% relative Lumpur component.
有利な酸は、例えば特に以下の組成での1,2−シクロヘキサンジカルボン酸、フタル酸及び/又はアジピン酸である:
1,2−シクロヘキサンジカルボン酸92〜100モル%及びフタル酸及び/又はアジピン酸0〜8モル%、又は
フタル酸60〜70モル%及びアジピン酸30〜40モル%。
Preferred acids are, for example, 1,2-cyclohexanedicarboxylic acid, phthalic acid and / or adipic acid, especially in the following composition:
92-100 mol% 1,2-cyclohexanedicarboxylic acid and 0-8 mol% phthalic acid and / or adipic acid, or 60-70 mol% phthalic acid and 30-40 mol% adipic acid.
有利なジオールは、例えばエチレングリコール(0〜40モル%)、2,2’−ジメチルプロパン−1,3−ジオール(35〜80モル%)、1,6−ヘキサンジオール(0〜15モル%)、トリメチロールプロパン(10〜25モル%)である。 Preferred diols are, for example, ethylene glycol (0-40 mol%), 2,2′-dimethylpropane-1,3-diol (35-80 mol%), 1,6-hexanediol (0-15 mol%). , Trimethylolpropane (10 to 25 mol%).
分枝鎖非晶質マクロポリオールは、15.0mgKOH/g未満、有利に10.0mgKOH/g未満、特に有利に0〜5mgKOH/gの酸価、並びに、0〜200mgKOH/g、有利に10〜150mgKOH/g、特に有利に30〜100mgKOH/gのヒドロキシル価を有することができる。 The branched amorphous macropolyol has an acid number of less than 15.0 mg KOH / g, preferably less than 10.0 mg KOH / g, particularly preferably from 0 to 5 mg KOH / g, and from 0 to 200 mg KOH / g, preferably from 10 to It can have a hydroxyl number of 150 mg KOH / g, particularly preferably from 30 to 100 mg KOH / g.
得られる数平均分子量Mnは、2500〜4500g/モル、有利に3000〜4000g/モルである。 The number average molecular weight M n obtained is 2500 to 4500 g / mol, preferably 3000 to 4000 g / mol.
酸価はDIN EN ISO 2114により測定される。 The acid value is measured according to DIN EN ISO 2114.
酸価(SZ)とは、物質1g中に含まれる酸の中和に必要な水酸化カリウムの量をmgで示したものと解釈される。試験すべき試料はジクロロメタン中に溶解され、0.1Nメタノール性苛性カリ液でフェノールフタレインに対して滴定される。 The acid value (SZ) is interpreted as the amount of potassium hydroxide required to neutralize the acid contained in 1 g of the substance in mg. The sample to be tested is dissolved in dichloromethane and titrated against phenolphthalein with 0.1N methanolic caustic potash.
ヒドロキシル価はDIN 53240−2により測定される。 The hydroxyl number is measured according to DIN 53240-2.
この方法の場合、試料と無水酢酸とを触媒としての4−ジメチルアミノピリジンの存在下に反応させ、その際、ヒドロキシル基をアセチル化させる。ここで、ヒドロキシル基1つにつき1分子の酢酸が生じ、引き続く過剰の無水酢酸の加水分解の間に酢酸が2分子生じる。酢酸の消費量を、滴定により、主要な値と、並行して実施すべきブラインド値との相違から測定する。 In this method, the sample and acetic anhydride are reacted in the presence of 4-dimethylaminopyridine as a catalyst, and the hydroxyl group is acetylated. Here, one molecule of acetic acid is produced per hydroxyl group, and two molecules of acetic acid are produced during the subsequent hydrolysis of excess acetic anhydride. The consumption of acetic acid is determined by titration from the difference between the main value and the blind value to be performed in parallel.
分子量を、ゲル浸透クロマトグラフィー(GPC)を用いて測定する。 Molecular weight is measured using gel permeation chromatography (GPC).
試料の特性決定を、溶離液としてのテトラヒドロフラン中でDIN 55672−1に従って測定する。 Sample characterization is measured according to DIN 55672-1 in tetrahydrofuran as eluent.
Mn(UV)=数平均分子量(GPC、UV検出)、g/モルでの表記
Mw(UV)=質量平均分子量(GPC、UV検出)、g/モルでの表記
本発明により得られた被覆された金属帯材は、有利な特性を示し、特に被覆系はT折り曲げ試験(T−ベンド)で2.0以下の値を示す。
M n (UV) = number average molecular weight (GPC, UV detection), notation in g / mol M w (UV) = mass average molecular weight (GPC, UV detection), notation in g / mol Coated metal strips exhibit advantageous properties, in particular the coating system exhibits a value of 2.0 or less in a T-bend test (T-bend).
本発明の要約
本発明の対象は、金属帯材を被覆するための、ポリエステルベースの分枝鎖非晶質マクロポリオールの使用である。使用される被覆材料は、以下の通り特徴付けられる:
芳香族及び/又は脂肪族ジカルボン酸及び/又はポリカルボン酸、例えばフタル酸、イソフタル酸、テレフタル酸、脂環式ジカルボン酸、例えば1,2−シクロヘキサンジカルボン酸、1,3−シクロヘキサンジカルボン酸、1,4−シクロヘキサンジカルボン酸及び/又はメチルテトラヒドロフタル酸、テトラヒドロフタル酸及び/又はメチルヘキサヒドロフタル酸、コハク酸、セバシン酸、ドデカン二酸、アジピン酸、アゼライン酸、ウンデカン二酸、ピロメリット酸、トリメリット酸、イソノナン酸及び/又は二量体脂肪酸、有利にイソフタル酸、1,2−シクロヘキサンジカルボン酸、フタル酸及び/又はアジピン酸の群からの少なくとも1のカルボン酸成分、
及び、
以下
1)少なくとも三官能性のアルコール10〜25モル%
と
2)少なくとも1の他のジオール75〜90モル%
とからの少なくとも1のアルコール成分を、
架橋試薬の存在下に反応させることにより得ることができ、以下
・2500〜4500g/モルのMn
・0〜200mgKOH/g、有利に20〜150mgKOH/g、特に有利に30〜100mgKOH/gのOH価、
・0〜10mgKOH/g、有利に0〜15mgKOH/g、特に有利に0〜5mgKOH/gの酸価
を特徴とするポリエステルベースの分枝鎖非晶質マクロポリオールが含有されている。
SUMMARY OF THE INVENTION The subject of the present invention is the use of polyester-based branched amorphous macropolyols for coating metal strips. The coating material used is characterized as follows:
Aromatic and / or aliphatic dicarboxylic acids and / or polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 4-cyclohexanedicarboxylic acid and / or methyltetrahydrophthalic acid, tetrahydrophthalic acid and / or methylhexahydrophthalic acid, succinic acid, sebacic acid, dodecanedioic acid, adipic acid, azelaic acid, undecanedioic acid, pyromellitic acid, At least one carboxylic acid component from the group of trimellitic acid, isononanoic acid and / or dimer fatty acids, preferably isophthalic acid, 1,2-cyclohexanedicarboxylic acid, phthalic acid and / or adipic acid,
as well as,
1) 10 to 25 mol% of at least trifunctional alcohol
And 2) 75-90 mol% of at least one other diol
At least one alcohol component from
It can be obtained by reacting in the presence of a cross-linking reagent, and the following: 2500 to 4500 g / mol of Mn
An OH number of 0 to 200 mg KOH / g, preferably 20 to 150 mg KOH / g, particularly preferably 30 to 100 mg KOH / g,
Polyester-based branched amorphous macropolyols characterized by an acid number of 0-10 mg KOH / g, preferably 0-15 mg KOH / g, particularly preferably 0-5 mg KOH / g are contained.
架橋試薬は、例えばポリイソシアネート及び/又はメラミン樹脂及び/又はその誘導体である。 The crosslinking reagent is, for example, a polyisocyanate and / or a melamine resin and / or a derivative thereof.
付加的に、ポリエステルベースの非晶質マクロポリオールを、被覆の際に、全組成物に対して0〜70質量%の助剤及び添加剤、特に、阻害剤、水及び/又は有機溶剤、中和剤、界面活性物質、酸素捕捉剤及び/又はラジカル捕捉剤、触媒、光安定剤、カラーブライトナー、光増感剤、チキソトロープ剤、皮張り防止剤、消泡剤、帯電防止剤、増粘剤、熱可塑性添加剤、染料、顔料、難燃剤、内部離型剤、充填剤及び/又は噴射剤と一緒に使用することができる。 In addition, polyester-based amorphous macropolyols can be coated with 0 to 70% by weight of auxiliaries and additives, in particular inhibitors, water and / or organic solvents, based on the total composition. Waxing agent, surfactant, oxygen scavenger and / or radical scavenger, catalyst, light stabilizer, color brightener, photosensitizer, thixotropic agent, anti-skinning agent, antifoaming agent, antistatic agent, thickening Can be used together with agents, thermoplastic additives, dyes, pigments, flame retardants, internal mold release agents, fillers and / or propellants.
被覆すべき金属に関しては何ら制限はなく、特に、金属帯材の金属はアルミニウム、鋼及び亜鉛を含む群から選択されている。 There are no restrictions on the metal to be coated, in particular the metal of the metal strip is selected from the group comprising aluminum, steel and zinc.
同様に、本発明の対象は、金属帯材を被覆するための方法において、被覆材料が、少なくとも1のカルボン酸成分、及び、アルコール成分に対して少なくとも三官能性のアルコール10〜25モル%と少なくとも1の他のアルコール75〜90モル%とからの少なくとも1のアルコール成分を、架橋試薬の存在下に反応させることにより得られたポリエステルベースの分枝鎖非晶質マクロポリオールからなり、その際、前記ポリエステルは、以下
・2500〜4500g/モルのMn
・0〜200mgKOH/gのOH価、及び
・0〜10mgKOH/gの酸価
を有し、その際、被覆材料を金属帯材に220℃未満の焼付温度( Peak Metal Temperature = PMT )で焼付ける方法である。
Similarly, the subject of the present invention is a method for coating a metal strip, wherein the coating material comprises at least one carboxylic acid component, and at least trifunctional alcohol 10-25 mol% with respect to the alcohol component. Consisting of a polyester-based branched amorphous macropolyol obtained by reacting at least one alcohol component from 75 to 90 mol% of at least one other alcohol in the presence of a crosslinking reagent, The polyester is as follows: 2500 to 4500 g / mol of Mn
・ Has an OH value of 0 to 200 mgKOH / g, and an acid value of 0 to 10 mgKOH / g, in which case the coating material is baked onto the metal strip at a baking temperature of less than 220 ° C. (Peak Metal Temperature = PMT) Is the method.
得られた金属帯材の被覆はT折り曲げ試験(T−ベンド)で2.0以下の値を示す。 The coating of the obtained metal strip shows a value of 2.0 or less in the T-bending test (T-bend).
本発明により使用されるポリエステルベースの分枝鎖非晶質マクロポリオールは、公知の方法で(Dr. P. Oldring著, Resins for Surface Coatings, 第III巻, Sita Technology出版, 203 Gardiness House, Bromhill Road, London SW 184JQ, England 1987を参照のこと)、出発酸及び出発アルコールの(半)連続的又は非連続的なエステル化により単段又は多段の運転方式で製造される。 The polyester-based branched amorphous macropolyol used in accordance with the present invention can be prepared in a known manner (Dr. P. Oldring, Resins for Surface Coatings, Volume III, Sita Technology Publishing, 203 Gardiness House, Bromhill Road. , London SW 184JQ, England 1987), prepared in a single or multi-stage mode of operation by (semi) continuous or non-continuous esterification of the starting acid and starting alcohol.
本発明により使用されるポリエステルベースの非晶質マクロポリオールの製造は、有利に不活性ガス雰囲気中で、150〜270℃、有利に180〜260℃、特に有利に200〜250℃で実施される。不活性ガスとして、窒素又は希ガス、特に窒素を使用することができる。不活性ガスは50ppm未満、特に20ppm未満の酸素含分を有する。理論的に算出された水量の大部分の分解後、真空で作業することができる。選択的に、(重)縮合反応の促進のための触媒及び/又は反応水を分離するための共沸添加剤の添加下に作業することもできる。典型的な触媒は、有機チタン化合物又は有機錫化合物、例えばチタン酸テトラブチル又は酸化ジブチル錫である。触媒は、選択的に、反応の開始時に他の出発材料と一緒に装入されてもよいし、又は後で反応の間に初めて装入されてもよい。共沸添加剤として、例えばトルエン又は種々のSolventNaphtha(R)品質を使用することができる。 The preparation of the polyester-based amorphous macropolyol used according to the invention is preferably carried out in an inert gas atmosphere at 150 to 270 ° C., preferably 180 to 260 ° C., particularly preferably 200 to 250 ° C. . Nitrogen or a noble gas, in particular nitrogen, can be used as the inert gas. The inert gas has an oxygen content of less than 50 ppm, in particular less than 20 ppm. After the decomposition of most of the theoretically calculated amount of water, it is possible to work in vacuum. As an alternative, it is also possible to work with the addition of a catalyst for the promotion of the (poly) condensation reaction and / or an azeotropic additive for separating the water of reaction. Typical catalysts are organotitanium or organotin compounds such as tetrabutyl titanate or dibutyltin oxide. The catalyst may optionally be charged with other starting materials at the beginning of the reaction, or may be charged for the first time during the reaction later. As an azeotropic additives can be used such as toluene or various SolventNaphtha (R) quality.
本発明により被覆された金属帯材は、同様に本発明の対象であり、かつ当業界の様式で任意に、特に、構造物において、及び建築物(例えば内部用途、屋根、壁)において、輸送物において、家庭用機器において、及び更なる加工において、例えば打抜き又は穿孔において使用することができる。 Metal strips coated in accordance with the present invention are also subject of the present invention and are transported optionally in the art, especially in structures, and in buildings (eg, internal applications, roofs, walls). It can be used in objects, in household equipment, and in further processing, for example in stamping or drilling.
たとえ他の実施態様が記載されていなくとも、当業者は上記記載を極めて広範囲で利用することができることが前提となっている。従って、有利な実施態様及び実施例は、単に記載されたものとして、また何らかの様式で限定された開示と理解されるべきではない。 It is assumed that those skilled in the art can utilize the above description in a very wide range even if no other embodiments are described. Accordingly, the advantageous embodiments and examples should not be construed as merely being described or as limiting in any manner.
以下に、本発明を実施例に基づいて詳説する。本発明の他の実施態様は同様に得ることができる。 Below, this invention is explained in full detail based on an Example. Other embodiments of the invention can be obtained as well.
実施例1
1,2−シクロヘキサンジカルボン酸無水物59.9部を、ネオペンチルグリコール7.5部、モノエチレングリコール10.3部、1,6−ヘキサンジオール13.2部及びトリメチロールプロパン9.1部と一緒に、最高250℃で窒素雰囲気中で、酸価1mgKOH/g未満及びヒドロキシル価55KOH/gが達成されるまで反応させる。ポリエステルを冷却後にSolvesso(R) 150/ブチルグリコール(3:1)中で65%溶解させる。 1,9.9 parts of 1,2-cyclohexanedicarboxylic anhydride, 7.5 parts of neopentyl glycol, 10.3 parts of monoethylene glycol, 13.2 parts of 1,6-hexanediol and 9.1 parts of trimethylolpropane The reaction is carried out together in a nitrogen atmosphere at a maximum of 250 ° C. until an acid number of less than 1 mg KOH / g and a hydroxyl number of 55 KOH / g are achieved. Solvesso After cooling, the polyester (R) 0.99 / butyl glycol (3: 1) to 65% dissolved in.
分析指標:
OHZ=55mgKOH・g-1、SZ=0.4mgKOH・g-1、Mn=3600g・mol-1
実施例2
OHZ = 55 mgKOH · g −1 , SZ = 0.4 mgKOH · g −1 , M n = 3600 g · mol −1
Example 2
1,2−シクロヘキサンジカルボン酸無水物55.2部を、ネオペンチルグリコール32.6部及びトリメチロールプロパン12.2部と一緒に、最高250℃で窒素雰囲気中で、酸価5mgKOH/gが達成されるまで反応させる。ポリエステルを冷却後にSolvesso(R) 150/ブチルグリコール(3:1)中で65%溶解させる。 An acid value of 5 mg KOH / g is achieved in 55.2 parts of 1,2-cyclohexanedicarboxylic anhydride together with 32.6 parts of neopentyl glycol and 12.2 parts of trimethylolpropane in a nitrogen atmosphere at a maximum of 250 ° C. React until Solvesso After cooling, the polyester (R) 0.99 / butyl glycol (3: 1) to 65% dissolved in.
分析指標:
OHZ=95mgKOH・g-1、SZ=5mgKOH・g-1、Mn=2500g・mol-1
実施例3
OHZ = 95 mgKOH · g −1 , SZ = 5 mgKOH · g −1 , M n = 2500 g · mol −1
Example 3
フタル酸34.6部及びアジピン酸15.1部を、ネオペンチルグリコール30.2部、モノエチレングリコール12.5部及びトリメチロールプロパン7.6部と一緒に、最高250℃で窒素雰囲気中で、酸価1mgKOH/g未満及びヒドロキシル価35KOH/gが達成されるまで反応させる。ポリエステルを冷却後にSolvesso(R) 150/ブチルグリコール(3:1)中で65%溶解させる。 34.6 parts phthalic acid and 15.1 parts adipic acid together with 30.2 parts neopentyl glycol, 12.5 parts monoethylene glycol and 7.6 parts trimethylolpropane in a nitrogen atmosphere at a maximum of 250 ° C. The reaction is continued until an acid number of less than 1 mg KOH / g and a hydroxyl number of 35 KOH / g are achieved. Solvesso After cooling, the polyester (R) 0.99 / butyl glycol (3: 1) to 65% dissolved in.
分析指標:
OHZ=35mgKOH・g-1、SZ=0.6mgKOH・g-1、Mn=4100g・mol-1
比較例A
OHZ = 35 mgKOH · g −1 , SZ = 0.6 mgKOH · g −1 , M n = 4100 g · mol −1
Comparative Example A
1,2−シクロヘキサンジカルボン酸無水物50部を、ネオペンチルグリコール48.8部及びトリメチロールプロパン1.2部と一緒に、最高250℃で窒素雰囲気中で、酸価5mgKOH/g未満及びヒドロキシル価47mgKOH/gが達成されるまで反応させる。ポリエステルを冷却後にSolvesso(R) 100中で65%溶解させる。 50 parts of 1,2-cyclohexanedicarboxylic anhydride together with 48.8 parts of neopentyl glycol and 1.2 parts of trimethylolpropane in a nitrogen atmosphere at a maximum of 250 ° C. with an acid number of less than 5 mg KOH / g and a hydroxyl number React until 47 mg KOH / g is achieved. Dissolving 65% After cooling, the polyester in Solvesso (R) 100.
分析指標:
OHZ=47mgKOH・g-1、SZ=4.0mgKOH・g-1、Mn=2100g・mol-1
比較例B
OHZ = 47 mgKOH · g −1 , SZ = 4.0 mgKOH · g −1 , M n = 2100 g · mol −1
Comparative Example B
1,2−シクロヘキサンジカルボン酸無水物53.5部を、ネオペンチルグリコール33.8部及びトリメチロールプロパン12.7部と一緒に、最高250℃で窒素雰囲気中で、酸価5mgKOH/g及びヒドロキシル価128mgKOH/gが達成されるまで反応させる。ポリエステルを冷却後にSolvesso(R) 150/ブチルグリコール(3:1)中で65%溶解させる。 53.5 parts of 1,2-cyclohexanedicarboxylic anhydride together with 33.8 parts of neopentyl glycol and 12.7 parts of trimethylolpropane in a nitrogen atmosphere at a maximum of 250 ° C. with an acid value of 5 mg KOH / g and hydroxyl The reaction is allowed to reach a value of 128 mg KOH / g. Solvesso After cooling, the polyester (R) 0.99 / butyl glycol (3: 1) to 65% dissolved in.
分析指標:
OHZ=128mgKOH・g-1、SZ=5mgKOH・g-1、Mn=2400g・mol-1
比較例C
OHZ = 128 mgKOH · g −1 , SZ = 5 mgKOH · g −1 , M n = 2400 g · mol −1
Comparative Example C
1,2−シクロヘキサンジカルボン酸無水物50部を、ネオペンチルグリコール36.8部及びトリメチロールプロパン13.2部と一緒に、最高250℃で窒素雰囲気中で、酸価5mgKOH/g及びヒドロキシル価110mgKOH/gが達成されるまで反応させる。ポリエステルを冷却後にSolvesso(R) 100中で65%溶解させる。 50 parts of 1,2-cyclohexanedicarboxylic anhydride together with 36.8 parts of neopentyl glycol and 13.2 parts of trimethylolpropane in a nitrogen atmosphere at a maximum of 250 ° C. with an acid number of 5 mg KOH / g and a hydroxyl number of 110 mg KOH React until / g is achieved. Dissolving 65% After cooling, the polyester in Solvesso (R) 100.
分析指標:
OHZ=110mgKOH・g-1、SZ=5.1mgKOH・g-1、Mn=2200g・mol-1
塗料配合物
OHZ = 110 mgKOH · g −1 , SZ = 5.1 mgKOH · g −1 , M n = 2200 g · mol −1
Paint formulation
1 例えばCytec Industries Inc.社製のCymel 303;前記架橋剤は、その反応性NH2基がメチロール基によりブロックされていることが特徴的であり、該基はコイルコーティング法において通常の高められた温度で分解され、かつポリエステルと反応し得る。 1 Cymel 303, for example from Cytec Industries Inc .; said cross-linking agent is characterized in that its reactive NH 2 groups are blocked by methylol groups, which groups are usually enhanced in the coil coating process Can decompose at temperature and react with polyester.
2 例えばKing Industries, Inc.社製のNacure 2500;前記酸性触媒(化学的にブロックされている)は、メラミン成分とポリエステル成分との反応を可能にするために必要である。 2 For example, Nacure 2500 from King Industries, Inc .; the acidic catalyst (chemically blocked) is required to allow the reaction of the melamine component with the polyester component.
3 Byk-Chemie社製のByk 350;レベリングの改善及び光沢の向上のためのアクリレート添加剤。該添加剤は塗膜にロングウェーブを付与しハジキを防止する。表面張力はわずかに低下するに過ぎない;リコート性及び層間密着性に悪影響はない。 3 Byk 350 from Byk-Chemie; acrylate additive for improved leveling and gloss. The additive imparts a long wave to the coating and prevents repellency. The surface tension is only slightly reduced; there is no adverse effect on recoatability and interlayer adhesion.
塗膜技術試験
方法:
1 ECCA試験法T11:(前記試験法により、基礎となる焼付条件下での反応性塗料系の架橋を試験することができる。)
実施:
アルミニウム又は亜鉛めっきされた鋼等からなる被覆された「薄板」に、メチルエチルケトン(MEK)中に浸漬させた綿球で(1又は2kgの重り(MEKハンマー)で)化学的及び/又は機械的に負荷をかける。該負荷は直線的なダブルストロークであり、その際、被覆の化学的な攻撃が生じ得る。通常、完全に硬化した被覆は、100ダブルストローク(DH)に問題なく耐え得る。完全硬化が十分でない場合、第一のダブルストローク後に、場合によりそれより後で(<100DH)、塗膜の溶解が生じる。相応して達成されたダブルストロークの数を書き留める。これは、例えば塗膜系の完全硬化又は架橋密度又は反応性のための一つの指標である。
Method:
1 ECCA Test Method T11: (By the above test method, the crosslinking of the reactive paint system under the basic baking conditions can be tested.)
Implementation:
Chemically and / or mechanically with a cotton ball soaked in methyl ethyl ketone (MEK) (with a 1 or 2 kg weight (MEK hammer)) on a coated “thin plate” made of aluminum or galvanized steel or the like Burdening. The load is a linear double stroke, where chemical attack of the coating can occur. Typically, a fully cured coating can withstand 100 double strokes (DH) without problems. If complete cure is not sufficient, dissolution of the coating occurs after the first double stroke, possibly later (<100 DH). Write down the number of double strokes achieved accordingly. This is one indicator for complete cure or crosslink density or reactivity of the coating system, for example.
2 Peak Metal Temperature(焼付工程の間に測定された薄板表面上の最高温度)
3 ECCA 試験法T5:前記作業指示の目的は、曲げ応力時の被覆の延性及び付着強度の評価である。試験体の亀裂のない曲げを許容する最小曲げ半径は、180°曲げでの抵抗を決定する。
2 P eak M etal T emperature (maximum temperature on the measured sheet surface during the baking step)
3 ECCA Test Method T5: The purpose of the work instruction is to evaluate the ductility and adhesion strength of the coating under bending stress. The minimum bend radius that allows crack free bending of the specimen determines the resistance at 180 ° bend.
実施:
未負荷の試験体のT折り曲げの試験
試験板は平らでかつひずみ(例えば折れ曲がり)のないものでなければならない。
Implementation:
Test of T-bending of unloaded specimens The test plate must be flat and free from strain (eg bending).
試験薄板を被覆と共に外側へ手で折り曲げ台を用いて約180°予め曲げる。 The test sheet is pre-bent about 180 ° together with the coating by hand using a folding table.
そのために、塗装面を有する幅最大10cmの薄板を、後方に、折り曲げ台の最も小さい間隙に挿入する。 For this purpose, a thin plate having a painted surface and a maximum width of 10 cm is inserted rearward into the smallest gap of the folding table.
次いで、予め折られた薄板をバイスで締めて固定し、エアギャップのないようにする。 Next, the thin plate that has been folded in advance is fastened and fixed with a vice so that there is no air gap.
曲げくびれ部を10倍拡大ルーペを用いて亀裂に関して試験する。 The bend neck is tested for cracks using a 10x magnifier.
その後、曲げくびれ部の全幅にわたってテサフィルム帯体を押し当て、急激に剥がし、付着した塗膜粒子を試験する。 Thereafter, the tether film strip is pressed over the entire width of the constricted neck, peeled off rapidly, and the coated film particles are tested.
最小曲げ半径(0T−0.5T−1T等)を測定し、その際、塗膜は亀裂を有していない(T−折り曲げ−亀裂)か、もしくはテサフィルム上に塗膜の剥げ(T−折り曲げ−付着)が認められない。 The minimum bend radius (0T-0.5T-1T, etc.) is measured. At that time, the coating film has no crack (T-bending-crack) or the coating film is peeled off on the tether film (T- Bending-adhesion) is not recognized.
Claims (17)
・2500〜4500g/モルのMn
・0〜200mgKOH/gのOH価、及び
・0〜10mgKOH/gの酸価
を有するものとする、使用。 At least one carboxylic acid component for coating the metal strip, and at least from 10 to 25 mol% of at least trifunctional alcohol and at least one other alcohol of 75 to 90 mol% with respect to the alcohol component. The use of a binder comprising a polyester-based branched amorphous macropolyol obtained by reacting one alcohol component in the presence of a crosslinking reagent, wherein the polyester comprises: 2500 to 4500 g / Mn Mn
Use, having an OH number of 0-200 mg KOH / g and an acid number of 0-10 mg KOH / g.
1,2−シクロヘキサンジカルボン酸92〜100モル%及びフタル酸及び/又はアジピン酸0〜8モル%、又は92-100 mol% 1,2-cyclohexanedicarboxylic acid and 0-8 mol% phthalic acid and / or adipic acid, or
フタル酸60〜70モル%及びアジピン酸30〜40モル%であることを特徴とする請求項3記載の使用。Use according to claim 3, characterized in that it is 60-70 mol% phthalic acid and 30-40 mol% adipic acid.
・2500〜4500g/モルのMn
・0〜200mgKOH/gのOH価、及び
・0〜10mgKOH/gの酸価
を有し、その際、被覆材料を金属帯材に220℃未満の焼付温度(PMT)で焼付ける方法。 In the method for coating a metal strip, the binder comprises at least one carboxylic acid component and at least trifunctional alcohol 10-25 mol% and at least one other alcohol 75-90 mol with respect to the alcohol component. % Of a polyester-based branched amorphous macropolyol obtained by reacting at least one alcohol component in the presence of a crosslinking reagent, wherein the polyester comprises: Mn of mole
A method of having an OH value of 0 to 200 mg KOH / g and an acid value of 0 to 10 mg KOH / g, wherein the coating material is baked onto the metal strip at a baking temperature (PMT) of less than 220 ° C.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE102006062041.0 | 2006-12-29 | ||
DE200610062041 DE102006062041A1 (en) | 2006-12-29 | 2006-12-29 | Coating metal tape, e.g. for cladding or vehicle parts, involves using coating material containing amorphous, branched macro-polyester-polyol and crosslinker and then stoving at moderate temperature |
PCT/EP2007/059643 WO2008080644A1 (en) | 2006-12-29 | 2007-09-13 | Method for coating metal bands |
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JP2010514553A JP2010514553A (en) | 2010-05-06 |
JP5264768B2 true JP5264768B2 (en) | 2013-08-14 |
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JP2009543402A Active JP5264768B2 (en) | 2006-12-29 | 2007-09-13 | Method for coating a metal strip |
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EP (1) | EP2094795B1 (en) |
JP (1) | JP5264768B2 (en) |
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CN (1) | CN101210151B (en) |
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CA (1) | CA2670066C (en) |
DE (1) | DE102006062041A1 (en) |
PL (1) | PL2094795T3 (en) |
RU (1) | RU2470971C2 (en) |
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DE102007038313A1 (en) * | 2007-08-14 | 2009-02-19 | Evonik Degussa Gmbh | Inorganically-modified polyester binder composition, process for its preparation and its use |
JP2010248326A (en) * | 2009-04-14 | 2010-11-04 | Basf Coatings Japan Ltd | Aqueous mid-coat paint composition |
CN102220072B (en) * | 2011-04-20 | 2015-09-09 | 镇江市万源电子有限公司 | Special coating material for aluminium strip insulating coating |
CN102229276A (en) * | 2011-04-20 | 2011-11-02 | 镇江市万源电子有限公司 | Aluminum strip with insulation coatings |
CN103980449B (en) * | 2014-04-30 | 2017-03-15 | 中国科学院化学研究所 | A kind of 3D printing composite and preparation method thereof |
DE102014218188B4 (en) | 2014-09-11 | 2023-01-19 | Evonik Operations Gmbh | Formulation for coating substrates, method for coating substrates, coated substrates and use of the formulation |
CN108084391A (en) * | 2016-11-21 | 2018-05-29 | 航天特种材料及工艺技术研究所 | A kind of polyurethane and preparation method thereof |
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JPH0635561B2 (en) * | 1985-04-12 | 1994-05-11 | 日本ペイント株式会社 | Coil coating coating composition |
DE19935539A1 (en) * | 1999-07-30 | 2001-02-08 | Herberts Gmbh & Co Kg | Process for producing weather-stable powder coatings |
AU6386301A (en) * | 2000-04-20 | 2001-11-07 | Akzo Nobel Nv | Branched hydroxyl-functional polyester resin and its use in aqueous cross-linkable binder compositions |
DE10233104A1 (en) * | 2002-07-20 | 2004-01-29 | Degussa Ag | Use of PU powder coatings for coil coating coatings with a matt appearance |
US7071267B2 (en) * | 2002-10-29 | 2006-07-04 | Basf Corporation | Polyester coil coating, process of coating a coil, and coated coil |
US6897265B2 (en) * | 2002-10-29 | 2005-05-24 | Basf Corporation | Polyester coil coating |
DE10322845A1 (en) * | 2003-05-19 | 2004-12-16 | Degussa Ag | Branched, amorphous macropolyols based on polyester with a narrow molecular weight distribution |
US20050287349A1 (en) * | 2004-06-23 | 2005-12-29 | Yu Poli C | Method for coating coils |
EP1726621A1 (en) * | 2005-05-26 | 2006-11-29 | Cytec Surface Specialties, S.A. | Thermosetting powder compositions |
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DE102006062041A1 (en) | 2008-07-03 |
RU2009128869A (en) | 2011-02-10 |
WO2008080644A1 (en) | 2008-07-10 |
SI2094795T1 (en) | 2014-04-30 |
EP2094795B1 (en) | 2013-12-04 |
KR101476467B1 (en) | 2014-12-24 |
AU2007341557B2 (en) | 2013-10-24 |
PL2094795T3 (en) | 2014-04-30 |
EP2094795A1 (en) | 2009-09-02 |
AU2007341557A1 (en) | 2008-07-10 |
CA2670066A1 (en) | 2008-07-10 |
KR20090094451A (en) | 2009-09-07 |
CN101210151A (en) | 2008-07-02 |
CN101210151B (en) | 2014-10-22 |
CA2670066C (en) | 2014-07-08 |
JP2010514553A (en) | 2010-05-06 |
US20100028697A1 (en) | 2010-02-04 |
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